Condensation products of the naphthoquinone-imine series



Patented May 15, 1951 A '7 r UNITED, STATES PATENT, oFncE CONDENSATION PRODUCTS OF THE NAPHTHOQUINONE-IMINE SERIES Valentin Kartas'chofi and Ernest Merian, Basel, Switzerland, assignors to Sandoz, A. G., Basel, I Switzerland, a Swiss firm No Drawing. Application February 13, 1950, Se-

rial No. 144,042. In. Switzerland February 24,

I 14- Claims (01. 260-163) 2 This invention relates to the preparation of It has further been ascertained that while thenew and valuablecompounds of the naphthocondensation products olcitainedv by condensing quinone-imine series. naphthazarine' intermediate: with only'one amiriQ-f It is known that if dinitronaphthaleneis' reas more fully described in U. S. Patent's' Nosyll duced in sulfuric acid a compound generally re- 5- 2,066,119 and 2,135,366 and having the general ferred to as naphthazarine intermediate havformula ing the formula H H IV H H 11111 or-according to the modern writing- X' being H, --OH, -'-NHz, O-alk'yl or *0- TT alkyl-O-H, are suitable for dyeing cellulose acetate to greenish-blue shades.

In our copending" application, Ser. No. 144,041, filed on even date herewith, there are described and claimed the condensation products obtained 1 by condensing naphthazarine intermediate with -an equivalent of aromatic aminoazo compound. They are suitable fordyein'g cellulose acetate and 15 produced that thls compound can be superpolyamides in beautiful green, yellowishand. superpolyamides', the results are only blue condensed with amines and further sulfonated to green, olive and brown Shades I meld dyestuffs mthasfurther been; ascertained that the hapljl. has been foupd that whlle condensa 3o thazarine intermediate can be halogenated, The n i q p l l by fpndensfmg the naph" reaction products are described and claimedxin mu h a more. copending application, Ser. No. 120,597 (continudescnbed U Patent 647370 ation of application Serial No. 729,401, filed Febhavmg the general formula ruary 18, 1947) and correspond to the general 11 formula 6 ins:

'X being --H; CH:,- or -NH2, are suitable for coloring oils, fats andw'axes including petroleum wherein at least one X stands for a halogen oi-l fractions such as gasoline, in beautiful green atom, the other X's being" hydrogen, According shades; and if sulfonated are useful as acid wool to depending application Ser.. No. 34,553, filed dyestufi's, they have practically no affinity for June 22; 1948, now Patent No. 2,538,005, issued.

celluloseacetate andsuperpolyamides. January 16, I941, orient the mtrogen atoms'o'f these compounds may be hydrolyzed to produce compounds corresponding to the formula wherein at least one X stands for a halogen atom, the other Xs being hydrogen.

It is an object of this invention to produce a new class of condensation products by condensing and similar ones.

In copending application, Ser. No. 743,195,

there is described and claimed the condensation of the halogenated naphthazarine intermediate (Ser. No. 729,401) with aromatic amines, such 2,553,050 g t f as aniline, p-toluidine, o-anisidine, aminohydroquinone dimethyl ether, benzidine, tetrahydro-pnaphthylamine, p-aminoacetanilide, cresidine, the resulting condensation products being blue, reddish blue and navy blue dyes for cellulose acetate and nylon.

However, the analogous condensation products (with aromatic amines) of halogenated and hydrolyzed naphthazarine intermediates accordin to application, Ser. No. 34,553, are worthless because of their lack of fastness to light.

It could therefore not be expected that also aminoazo compounds can easily be condensed with these halogenated intermediates to get valuable dyestuffs of various shades besides blue, reddish blue and navy blue, which are considerably fast to light, to washing and togas-fumes. It is furthermore very surprising that these new condensation products have such a great aflinity for cellulose acetate and superpolyamides though they are halogenated'and though they have such a high molecular weight.

It is a further object of this invention to dye cellulose ester fibers, synthetic polyamide fibers and polyurethane fibersfin green, olive, brown and grey shades. Up to now these'shades were produced either by using dyestuff mixtures of the dispersed type, i. e. mixtures of yellow and blue dyestuffs, or by dyeing cellulose acetate and superpolyamides with aromatic aminoazo compounds followed by diazotizing and developing with suitable coupling compounds, this process being very complicated. Dyestuff mixtures of the dispersed type, moreover, have the disadvantage that, depending upon the method of dyeing, different shades are obtained being sometimes more yellow, sometimes more blue. more, these mixtures'are either fast to light or fast to gas-fumes, according to the blue component employed. 7 v 7 These green, olive, brown and grey shades, obtainable with uniform dyestuifs of the dispersed type, are of good fastnesses to light and to gasfumes and can be discharged in light shades giving a pure white.

As aminoazo compounds suitable for condensation with the halogenated naphthazarine intermediates mentioned above, the most varied substituted derivatives of the general formula far as these compounds have not been previously described, they can be obtained by coupling diazotized nitroanilines with the desired coupling components and subsequent reduction of the nitro group with e. g. sodium sulphide or sodium sulfhydrate or by coupling dia zotized aminoacet-e Furtheranilides or any other aminoacylanilides followed by a hydrolysis of the acylamino group.

The condensation with the naphthoquinoneimine is advantageously carried out in the presence of a solvent which is indilferent to the reaction compounds, such as e. g. acetic acid, propionic acid, ethanol, isopropanol, and dilute acetic acid, at an elevated temperature and may also advantageously be carried out in presence of a condensation accelerator such as boric acid, copper, copper salts, sodium acetate and the like.

The new condensation products thus obtained correspond to the general formula B; being acar'bocy'clic' or a heterocyclic radical and V Z1, Z Z3 being hydrogen or substituents other than sulfonic acid groups.

These new compounds dissolve in organic solvents with green, olive, grey or brown colors. They can be used either as dyestuffs for cellulose ester fibers, synthetic polyamide and polyurethane fibers or as intermediates for the preparation of other dyestuffs.

The following examples illustrate how the invention may be carried out in practice, butthey are in no way limitative. Parts are by weight and temperatures in degrees centigrade.

EXAMPLE 1 200 parts of finely powdered 3.7-dibromo-5- amino-8-hydroxy-l.4-naphthoquinone 1 imine are stirred in 450 parts of glacial acetic acid and treated at 60 with 120 parts of 4-aminoazobenzene. After 6 hours it will be found that a sample, when placed on filter paper, gives a blackish green residue and a green solution. The product is poured onto 1500 parts of icewater and filtered. After washing out a small excess of 4-aminoazobenzene and drying, a powder is obtained which dyes acetate silk and nylon in pure green shades. The new dyestuff corresponds to the formula If 80 parts of crystalline sodium acetate are added to the reaction mass, the condensation takes place more rapidly. In this case, the ob' tained dyestuff dyes acetate silk and nylon in somewhat bluer shades. It corresponds to a mixture of and more yellow than that of the first example. The new dyestufi corresponds to the formula CH3 CH3 I I I l EXAMPLE 3 87 parts of the halogenated naphthoquinoneimine used in the first example, 300 parts of glacial acetic acid and 72 parts of 4-amino-4- nitro-azobenzene are stirred for 1 hour at 90. Then the product is worked up in the same way as that of the preceding examples. The new compound which corresponds mainly to the formula 7 colors cellulose acetate. in yellowish olive and nylon in brown shades.

EXAMPLE 4 35 parts of the halogenated naphthoquinoneimine used in the first example are warmed in 300 parts of glacial acetic acid up to 80-90", when 23 parts of 4-amino-2'-hydroxy-5'-methyl-azobenzene are introduced. The temperature is kept at 80-90 for another 2 hours and then the product isolated as fully described above. The new condensation product dyes cellulose acetate and nylon in pure green shades. It is distinguished especially by its great dyeing power. The principal product of the dyestufi has the formula OH H EXAMPLE 5 35 parts of the halogenated naphthoquinoneimine of Example 1 are warmed in 300 parts of glacial acetic acid up to 80-90", when 29 parts of 4 amino -4' -ethylhydroxyethylamino-azobenzene are introduced. Then the temperature is slowly raised to 100-105. After 2 hours the reaction mass is poured onto ice-water and isolated in the usual way. A dark powder is obtained, which dyes cellulose acetate in brown and nylon in brownish purple shades. It consists mainly of CED-OH i b \H) EXAMPLE 6 35 parts of 3.7-dibromo-5.8-dihydroxy-l.4- naphthoquinone-l-imine are stirred up in 300 parts by glacial acetic acid at 80-90, when 22 parts of 4-aminoazobenzene are introduced. The temperature is raised up to 105 and condensation continued for 2 hours. Then the reaction mass is poured onto ice-water, vfiltered, washed free from acid and from a small excess of 4-aminoazobenzene. The new dyestuff colors cellulose acetate in grey and nylon in greybrown shades. It consists of a mixture of When 29 partsof l-aminoi-nitro-azobenzene I are taken in place of the 4-aminoazobenzene in the preceding example, there is obtained mainly the dyestuif of the formula The new compound dyes acetate silk in sepia and nylon in reddish-brown shades.

EXAMPLE 8 When the 4-aminoa zobenzene in Example 6 is replaced by 29 parts of 4-amino-4-ethylhydroxyethyl-amino-az0benzene, the principal reaction product has the following formula:

The new dyestuff colors cellulose acetate in redbrown and nylon in Bordeaux shades.

EXAMPLE 9 35 parts of 3.7-dibromo-5-amino-8-hydroxy- 1.4-naphthoquinone-1-imine are stirred in 300 parts by glacial acetic acid and treated at with 25.7 parts of 4'-ethoxy-4-amino-2-hydroxyazobenzene. After 3 hours it will be found that a sample is soluble in ethanol with a yellowish green coloration. The product is poured onto 1500 parts of ice-water and filtered. After wash-- ing and drying, a powder is obtained which dyes acetate silk and nylon in green shades. When the reaction is carried out in glacial acids, condensation generally takes place with the imino group in the a-IJOSitiOIl, while it takes place also with the halogen atom in the p-position when the reaction medium is diluted with water, alcohol or even more when a rather alkaline catalyst such as sodium acetate is used. The following tables summarize the properties of additional series of condensation products, made by proceeding according to the foregoing examples. Additional condensation products within the purview of the invention can be prepared by using the other halogenated naphthis application.

Table I Color of the sol.

Ammoazo compound used for condensation with 3.7-dibromo-d-ami- Color of the solug g sgg gggggg Color of dyeing Color of dyeing ii'lo-8-illilgdroxy-lA-naphthoqumone t1on in ethanol sulfuric acid or p frma1de on acetate silk 2 on nylon hyde 4-aminoazobenzene pure green yellow-green. pure green ,pure green. 4-aminoazotoluene yellowish green yellow yellowish green reen. 4-amino-4-nitro-azobenzene do green yellowish olive.. rown. 4-abmino-2-hydroxy-5-methyl-azopure green reddish brown. pure green. pure green.

enzene. 4-aminol-34-ethyl-hydroxyethylamiyellowish brown yellowish brown brown brownish purple.

no-azo enzene.

A-amino-Z-hydroxy-azobenzene pure green g. d o do green green.

4'=ethoxy-41amin0-2-hydroxy-azobenyellowish green. carmme lilac do grey-green.

zene.

4-aminobenzene-azo-naphthalene-(l). bluish green ol1-ve.. blue-grey greenishlblueuu blue-green.

aniline(-()%'-ezo-4)-(3-mcthylpyrazogreenish blue.,. redd1sh-yellowblue-green blucm blue-green.

'lone- 5 Table II Golor ofthe solu- Aminoazo compound used for conden- Color of the solution in 00110. i

sation with 3.7-dibromo-5.8-di-hygg g gfi ggi tion in cone. sulfuric acid 3 2 13? C0101 of l droxy-lA-naphthoquinone-l-imine l sulfuric acld .on'addition'of n ace a e Qn ny on p-formaldehyde i-aminoazobenzeneu V grey-green w yellowrgreenun grey-green grey rey-b ow 4aamiuoy-nitro azobenzene brownish greem. red-brown brown sepiareddish brown.

4-amibi1o-4 -ethy1-hydroxyethy1aminoreddish brown.. reddish brown.,. yellow-brown red-brown Bordeaux.

azo enzene. 4-amin0-2-hyd10Xy-azobenzene yellow-groom... brown red brown olive brown-olive,

4-aminobenzene-azonaphthalene-(l)mblue-grey 1112c blueiolet reddish blueblue-grey.

gebe nzene-azonaphthylamine-(1), brown-Qliv cherr r d-mw red-vi let brown. brown.

While the dye compounds of theinvention have been described more particularly in connection with the coloration of cellulose acetate and nylon textile materials, it is to be noted that they are useful for the coloration of the other materials named herein and that they yield about the same colors on these materials as they do on cellulose acetate and nylon.

These colors may be advantageously directly applied to the material undergoing coloration in the form of an aqueous suspension which can be prepared by milling the dye together with a suitable dispersing agent, such as e. g. the condensation of fl-naphtha'lene-sulfonic' acid and formal-- dehyde, a sulfonatcd aliphatic alcohol or soap, in presence of common salt, sodium sulfate 1. e. to get .more eflicient milling and by grinding said mixture to a paste in the presence of a sulfonated oil, soap or other suitable dispersing agent and dispersing the resulting paste in water. In some instances, the dye may possess su-fficient solubility in water as to render the use of a dispersing agent unnecesssary. Generally speaking, however, the use of a dispersing agent is desirable.

Direct dyeing operations can, with advantage, be conducted at temperatures ,of about 60-85, but any suitable temperature may be used, 7 Thus, the textile material to be dyedlor colored is ordinarily added to the dye-bath at a temperature lower than that at which the .mainportion of the dyeing is to be efiected, a temperature approximating -55", for example, following which the mpe ature is rai edto that selected for carrying out the dyeing operation. The temperature at which the dyeing is conducted may of course be varied somewhat depending upon the particular material undergoing coloration, As is understood by those skilled in the art, the intensity of dyeing can be varied by vary ,g the proportion of dye to material undergoing coloration,

Generally speaking 0.14% by weight of dye to material i employed although any desired proportions .can be used.

The following example is given to illustrate :a method for applying such colors to cellulose ace .tate fibers:

EXAMPLE 10 40 parts of the insoluble dye of Example l are milled together with 40 parts of the sodium salt of a fatty alcohol sulfonate and 20 parts of sodium sulfate. The powder thus obtained is mixed first with the same weight of a highly sulfonated turkey red oil into a 'fine paste, upon which water of "60 is poured. The whole is stirred until uniform dispersion is obtained, when it is added to the dye-bath through a sieve. The volume of dye-liquor is 1:20 on the weight of the material, the dye-bath being made up with the requisite amount of color and 2 grams of a fatty alcohol sulfonate per liter. 'The material is entered at 40-50% the temperature is slowly raised to and dyeing is continued'at this temperature for 1 hour. After dyeing the goods are Well washed off. One obtains pure greenshades fast to light, to gas-fumes and to washing.

The process, as precedingly disclosed, for the dyeing of cellulose acetate, can be used in applying the dyes of the present invention to other cellulose ester fibers, to synthetic polyamide fibers and to polyurethane ,fibers.

As set forth in the aforesaid application Ser. No. 120,597, the starting compounds wherein Y is NHfor example the starting compound of Example 1, namely, 3.7-dibromo-5-amino-:8hydroxy-l.4-naphthoquinone-leiminwmay be pre-' pared as follows;

'10 parts of .1 .S-dinitronaphthalene and 2.8 parts of .sulfur are added to 200 parts of sulfuric acid monohydrate, whereupon 40 parts of ,olenm (40% S03) are allowed to run in at .30".- This :aqsaoao 11 1 results in the formation of the naphthoquinonee imine 37.6 parts of the latter are then suspended in 500 parts of glacial acetic acid and heated to 65 while stirring thoroughly. After addition of 32.8 parts of anhydrous sodium acetate to the suspension, 64 parts of bromine are introduced dropwise in the course of 45 minutes. Stirring is continued at the same temperature for another half hour. While the naphthoquinone-imine is going into solution, the desired halogenated derivative separates out as a powder and may be isolated by filtration in the cold.

The other corresponding starting compounds may be obtained in analogous manner.

The starting compounds wherein Y is O--for example the starting compound of Example 6,.

3.7-dibromo 5.8 dihydroxy-1.4-naphnamely, thoquinone-l-iminemay be prepared according to the indications of the aforesaid application Ser. No. 34,553, as follows:

90 parts of a paste containing 25 parts of 3.7- dibromo 5-amino-8-hydroxy 1.4 naphthoquinone-vl-imine, the other 65 parts being water, are dissolved in 280 parts of sulfuric acid (94%) and the whole heated to 80 C. At this temperature the-'r nass is stirred for 50 minutes, and then the reaction mixture is poured into ice-water, filtered, and washed until freefrom acid. The product is the desired 3.7-dibromo-5.8 dihydroxy- 1.4-naphthoquinone-l-imine.

The other corresponding starting compounds may be obtained in analogous manner.

Having thus disclosed the invention what is claimed is:

1. A process for the manufacture of a condensation product of the naphthoquinone-imine series comprising the step of condensing a halogenated naphthazarine intermediate of the general formula wherein at least one X stands for a member of the group consisting of chlorine and bromine, the other X being hydrogen, and wherein -Y stands for a member selected from the group consisting of O- and NH, in a solvent with an equimolecular quantity of an aromatic aminoazo compound free from sulfonic acid groups, at a temperature of at least 60.

2. A process for the manufacture of a condensation product of the naphthoquinone-imine series, comprising the step of condensing a halo- 12 genated naphthazarine intermediate of the general formula N 6 NE Y SH wherein at least one X stands for a member of the group consisting of chlorine and bromine, the other X being hydrogen, and wherein --Y- stands for a member selected from the group consisting of O and NH in a solvent with an equimolecular quantity of an aromatic aminoazo compound which corresponds to the formula wherein R2 stands for a member selected from the group consisting of phenyl, naphthyl and pyrazolyl radicals, and wherein Z1, Z2 and Z3 stand for members selected from the group consisting of hyrogen, lower alkyl, hydroxy, nitro, lower alkoxy and lower alkyl-lower-hydroxyalkylamino, at a temperature of at least 60.

3. A process for the manufacture of a new condensation product of the naphthoquinone-imine series, comprising the steps of condensing 3.7-dibromo-5-amino-8-hydroxy-1'.4-naphthoquinonel-imine in a solvent with p-amino-azobenzene at a temperature of at least 60.

4. A process for the manufacture of a new condensation product of the naphthoquinone-imine series, comprising the step of condensing 3.7-dibromo-5amino-8-hydroxy-1.4-naphthoquinonel-imine in a solvent with 4-amino-4-ethylhydroxyethylaminoazobenzene at a temperature of at least 60.

5. A process for the manufacture of a new condensation product of the naphthoquinone-imine series, comprising the step of condensing 3.7-dibromo-5.8 dihydroxy 1.4 naphthoquinone-limine in a solvent With 4-amino-4-ethylhydroxyethylaminoazobenzene at a temperature of at least 60.

6. The condensation products of the naphthoquinone-imine series, corresponding to the general formula wherein Y stands for a member selected from the group consisting of O and NH, R2 stands for a member selected from the group consisting of phenyl, naphthyl and pyrazolyl radicals, and Z1, Z2 and Z3 represent members selected from the group consisting of hydrogen, lower alkyl, hydroxy, nitro, lower alkoxy and lower alkyl-lowerhydroxyalkylamino. l

13 7. The condensation products of the naphthoquinone-imine series, corresponding to the general formula wherein Y stands for a member selected from the group consisting of O and NH, and Z1, Z2 and Z3 stand for members selected from the group consisting of hydrogen, lower alkyl, hydroxy, nitro, lower alkoxy and lower alkyl-lower-hydroxyalkylamino.

8. The condensation product of the naphthoquinone-imine series of the formula 9. The condensation product of the naphthoquinone-imine series of the formula 10. The condensation product of the naphthoquinone-imine series of the formula 11. The condensation product of the naphthoquinone-imine series of the formula 12. The condensation product of the naphtho- 15 quinone-imine series of the formula OH I Br- CH3 13. A process for the manufacture of a new condensation product of the naphthoquinoneimine series, comprising the step of condensing 3.7-dibromo-5-amino- 8-hydroxy 1.4 naphtho quinone-l-imine in a solvent with a-amino-azotoluene at a temperature of at least 60.

14. A process for the manufacture of a new condensation product of the naphthoquinoneimine series, comprising the step of condensing 3.7-dibromo-5-amino 8 hydroXy-1.4-naphthoquinone-l-imine in a solvent with 4-amino-2- hydroxy-5'-methyl-azobenzene at a temperature of at least 60. 

9. THE CONDENSATION PRODUCT OF THE NAPHTHOQUINONE-IMINE SERIES OF THE FORMULA 